Composition for shaping keratin fibers containing starches modified with propylene oxide

ABSTRACT

Cosmetic agents for temporarily reshaping keratin fibers, particularly human hair, containing in a cosmetic carrier at least one starch modified with propylene oxide, the starch having an average molecular weight (weight-average) of 50 to 2,500 kDa and a propylene oxide content of 4 to 6 wt. % (based on weight of the starch modified with propylene oxide), wherein the agents achieve styling with a good degree of hold and elevated flexibility. The propylene oxide-modified starches are based on renewable raw materials. Here, effective styling agents for hair can be provided without having to rely on setting polymers obtained from fossil fuels.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of International ApplicationNo. PCT/EP2010/065862 filed 21 Oct. 2010, which claims priority toGerman Patent Application Nos. 10 2009 045 925.1 and 10 2009 045 933.2,both filed 22 Oct. 2009, each of which are incorporated herein byreference.

The present invention relates to cosmetic agents for temporarilyreshaping keratin fibers, containing in a cosmetic carrier at least onestarch modified with propylene oxide and having an average molecularweight (weight-average) of 50 to 2,500 kDa and a propylene oxide contentof 4 to 6 wt. % (based on weight of the starch modified with propyleneoxide).

Agents for temporary shaping typically contain synthetic polymers as theshaping component. Preparations containing a dissolved or dispersedpolymer can be applied to hair by propellant gases or by a pumpmechanism. Hair gels and hair waxes, however, are generally not applieddirectly onto the hair but are rather distributed in the hair using acomb or the hands.

Synthetic polymers typically used in agents for temporary shaping areproduced from appropriate synthetically obtainable monomers. Thesemonomers are obtained from fossil substances such as petroleum byconversion into the corresponding polymer building blocks, inter aliawith input of energy. In a more sustainable approach to nature as ourhabitat and to resources, it remains desirable to use only thosecosmetic raw materials for cosmetic products which can be obtained from“renewable” raw materials using the least possible energy. However,synthetic polymers can only be reduced in quantity or substituted if thereplacement provides the characteristics desired for the intendedapplication and ensures that the keratin-containing fibres adequatelymaintain a stable shape.

Moreover, naturally based replacement polymers should maintain thebounce and silkiness of keratin-containing fibers which have been set inshape. Formation of polymer particles which are visible to the naked eyeon keratin-containing fibers must be avoided. Furthermore, thekeratin-containing fibers must not look dull, but should instead have anatural gloss.

The present invention provides a cosmetic composition with ashape-setting action which brings about improved or equivalent shapesetting and does not exhibit the above-stated disadvantages. In sodoing, it is intended to make little or, if possible, no use ofsynthetic polymers based on fossil raw materials.

The present invention accordingly firstly provides a cosmetic agent fortemporarily reshaping keratin fibers, particularly human hair,containing in a cosmetic carrier at least one starch modified withpropylene oxide, wherein the starch has an average molecular weight(weight-average) of 50 to 2,500 kDa and a propylene oxide content of 4to 6 wt. % (based on weight of the starch modified with propyleneoxide). These agents exhibit excellent parameters for use on hair. Thestarch can be incorporated into the agents by simple mixing virtuallywithout input of heat at a temperature of at most 30° C.

Keratin fibers according to the invention refer to furs, wool, feathersand particularly human hair.

Starch is a storage carbohydrate which is stored by many plants in theform of starch grains (granules) ranging in size from 1 to 200 μm invarious plant parts, for example, in tubers or roots, cereal seeds,fruits and in the medulla. Starch modified with propylene oxide whichcan be used according to the invention can be obtained from starch frompotatoes, maize, rice, peas, acorns, chestnuts, barley, wheat, bananas,sago, millet, sorghum, oats, barley, rye, beans, sweet potato, arrowrootor manioc. Particularly pronounced effects according to the inventionare achieved using tapioca starch modified with propylene oxide, potatostarch modified with propylene oxide or mixtures of both of thesestarches. It is very particularly preferred to use potato starchmodified with propylene oxide as the corresponding modified starch.

Starch belongs to the homoglycan family and is a polycondensationproduct of D-glucose. Starch consists of three structurally differentpolymers: d-glucopyranose, namely amylose, amylopectin and an“intermediate fraction”. Higher plants contain 0 to 45 wt. % of amyloserelative to dry solids.

The intermediate fraction, also referred to as “abnormal amylopectin”,lies structurally between amylose and amylopectin. The quantities statedfor amylopectin for the purposes of the present application include theintermediate fraction.

It is preferred for the starch modified with propylene oxide to have anamylose content of less than 25 wt. %, particularly less than 20 wt. %,based on total weight of the starch. It was found that, in order toachieve the effect according to the invention, a particularly suitablestarch is one having 17 to 22 wt. % amylose and 78 to 83 wt. %amylopectin.

Amylose consists of predominantly linear α-1,4-glycosidically linkedd-glucose M_(r) 50,000-150,000. The resultant chains formation doublehelices in the starch.

In addition to the α-1,4 linkages described for amylose, amylopectinalso contains from 4 to 6% of α-1,6 bonds as branch points. The averagedistance between the branch points amounts for instance to 12 to 17glucose units. The molar mass of 10⁷ to 7·10⁸ corresponds to approx. 10⁵glucose units, amylopectin accordingly being among the largestbiopolymers. Said branches are distributed within the molecule in such away that a cluster structure with relatively short side chains develops.Two of these side chains in each case form a double helix. Due to thenumerous branch points, amylopectin is relatively readily soluble inwater.

According to the invention, a starch modified with propylene oxide istaken to mean a reaction product of a starch with propylene oxide. Sucha reaction product comprises at least one structural unit of formula(I),

wherein at least one of R, R′ or R″ is a group of the formula

where n 0 andat most 2 of R, R′, R″ are a hydrogen atom. A bond marked with thesymbol * in the formulae of the present application corresponds to afree valence of the corresponding structural unit. Starches modifiedwith propylene oxide are, for example, prepared by reacting a nativestarch with propylene oxide. Prior to modification with propylene oxide,the starch may have been subjected to various physical or chemicalprocesses such as heat treatment, shearing or cleavage by thermaltreatment, acid hydrolysis, oxidation, or enzymatic treatment, etc.

It is preferred for the starch modified with propylene oxide when usedin the agent according to the invention not to be present as individualstarch grains (granules). Accordingly, the starch grains are opened up,for example, by heat or shearing, and the corresponding polysaccharidemolecules are released therefrom. The released polysaccharide moleculescan be modified with propylene oxide after or before release.

In a preferred embodiment, the propoxylated starch is gelatinized. If anaqueous suspension of starch is heated or compressed at a criticaltemperature or pressure, tangential swelling of the bodies is observedaccompanied by loss of birefringence, a modified X-ray structure and anabrupt increase in the viscosity of the solution. This phenomenon isknown as gelatinization.

Starches according to the invention modified with propylene oxide arepresent in the agent in a molecular weight distribution. Molecularweight distribution is determined experimentally by gel filtrationchromatography against dextran. One important feature of the inventionis the weight-average molecular weight of the propylene oxide-modifiedstarches present in the agent. This weight-average is an averagemolecular weight which takes account of the total weight of themolecules of different molecular weight, and not merely the number ofmolecules. The “weight fraction”

w _(i)=(N _(i) M _(i))/[Σ(N _(i) M _(i))]

is first defined in order to calculate the weight average statistically.This indicates the proportion by weight of macromolecules in the sampleconsisting of i segments (e.g., monomer building blocks) of mass M_(i)consist and occur N_(i) times in the sample. The following equationaccordingly applies to the weight-average molecular weightM_(w)=Σw_(i)M_(i):

M _(w)=[Σ(N _(i) M ² _(i))]/[Σ(N _(i) M _(i))].

Particularly preferred agents are those having starches modified withpropylene oxide and which have an average molecular weight(weight-average) of 100 to 2,000 kDa, particularly 500 to 1,800 kDa,very preferably 700 to 1,000 kDa.

It is particularly preferred for the starch modified with propyleneoxide to be uncrosslinked. Crosslinking of starch modified withpropylene oxide is present when the linear or branched polysaccharidemacromolecules of the starch are covalently linked by a crosslinkingagent to form a three-dimensional, insoluble polymer network which isthen only swellable. Native starch is generally regarded asuncrosslinked and, should crosslinking be desired, would requireartificial crosslinking by chemical synthesis. Such artificialcrosslinking can be carried out with crosslinking agents such asepichlorohydrin. (Propylene oxide-modified) starches which do notexhibit such crosslinking are uncrosslinked.

In order to achieve a lower molecular weight, for example, 100 to 400kDa or 200 to 300 kDa, the starches are subjected to mechanicalcleavage, enzymatic cleavage (particularly with α-amylase, β-amylase,glucoamylase or debranching enzymes), cleavage by acid hydrolysis(particularly with hydrochloric acid, sulfuric acid or phosphoric acid),thermal cleavage or reaction with oxidizing agents (such as periodate,hypochlorite, chromic acid, permanganate, nitrogen dioxide, hydrogenperoxide or organic percarboxylic acid, preferably with hydrogenperoxide). Kneaders, extruders, stator/rotor devices and/or stirrers aresuitable for mechanically cleaving starch.

Oxidative cleavage using hydrogen peroxide is preferably suitable. Toaccomplish this, starch modified with propylene oxide is placed inwater, heated to 50 to 70° C., hydrogen peroxide is added, and themixture stirred at 70 to 85° C. for 2 to 5 hours.

The starch's propylene oxide content has an impact on styling hold andstyling flexibility as well as on the stability of the cosmetic agent.It has surprisingly been found that ideal application parameters areobtained when the modified starch has, based on weight of the starch, apropylene oxide content of 4 to 6 wt. %. Propylene oxide content can,for example, be determined, once Hodges cleavage has been carried out,according to DIN EN 13268.

It has furthermore been found that cosmetic agents which are ideallysuitable for the invention are those in which, in a 43 wt. % solution inwater (i.e., a 43 wt. % aqueous solution), the modified starch exhibitsa viscosity from 150 to 1,500,000 mPa·s (Brookfield viscometer, spindle#7 at 20° C. and 20 rpm). Ideally suitable propylene oxide-modifiedpolysaccharides exhibit viscosities of 3,000 to 200,000 mPa·s,particularly 10,000 to 100,000 mPa·s, very preferably 40,000 to 70,000mPa·s (measured under the above-stated conditions).

It is preferred for the cosmetic agent to contain the polysaccharidemodified with propylene oxide in an amount of 0.01 wt. % to 40 wt. %,more preferably 0.5 wt. % to 10 wt. %, very preferably 2 wt. % to 6 wt.%, based on total weight of the agent.

Agents according to the invention preferably comprise foams or gels asthe cosmetic carrier and therefore are preferably in the form of a foamor gel. Excellent setting can be achieved with the starches.Furthermore, gels produced with the modified starches additionallyachieve superb transparency.

Very particularly preferred cosmetic agents according to the inventioncomply with at least one of the following embodiments A) to R):

A): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 50 to 2,500 kDa and apropylene oxide content of 4 to 6 wt. % (based on weight of the modifiedstarch).

B): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 700 to 1,000 kDa and apropylene oxide content of 4 to 6 wt. % (based on weight of the modifiedstarch).

C): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 50 to 2,500 kDa, apropylene oxide content of 4 to 6 wt. % (based on weight of the modifiedstarch) and a viscosity of 3,000 to 200,000 mPa·s (in a 43 wt. % aqueoussolution, Brookfield viscometer, spindle #7 at 20° C. and 20 rpm).

D): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 50 to 2,500 kDa, apropylene oxide content of 4 to 6 wt. % (based on weight of the modifiedstarch) and a viscosity of 10,000 to 100,000 mPa·s (in a 43 wt. %aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

E): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 700 to 1,000 kDa, apropylene oxide content of 4 to 6 wt. % (based on weight of the modifiedstarch) and a viscosity of 3,000 to 200,000 mPa·s (in a 43 wt. % aqueoussolution, Brookfield viscometer, spindle #7 at 20° C. and 20 rpm).

F): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 700 to 1,000 kDa, apropylene oxide content of 4 to 6 wt. % (based on weight of the modifiedstarch) and a viscosity of 10,000 to 100,000 mPa·s (in a 43 wt. %aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

G): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked tapioca starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 50 to 2,500 kDaand a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch).

H): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked tapioca starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 700 to 1,000 kDaand a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch).

I): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked tapioca starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 50 to 2,500 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 3,000 to 200,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

J): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked tapioca starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 50 to 2,500 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 10,000 to 100,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

K): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked tapioca starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 700 to 1,000 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 3,000 to 200,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

L): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked tapioca starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 700 to 1,000 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 10,000 to 100,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

M): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least onepotato starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 50 to 2,500 kDa and apropylene oxide content of 4 to 6 wt. % (relative to the weight of thestarch modified with propylene oxide).

N): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least onepotato starch modified with propylene oxide, the starch having anaverage molecular weight (weight-average) of 700 to 1,000 kDa and apropylene oxide content of 4 to 6 wt. % (based on weight of the modifiedstarch).

O): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked potato starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 50 to 2,500 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 3,000 to 200,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

P): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked potato starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 50 to 2,500 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 10,000 to 100,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

Q): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked potato starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 700 to 1,000 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 3,000 to 200,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

R): A cosmetic agent for temporarily reshaping keratin fibers,particularly human hair, comprising in a cosmetic carrier at least oneuncrosslinked potato starch modified with propylene oxide, the starchhaving an average molecular weight (weight-average) of 700 to 1,000 kDa,a propylene oxide content of 4 to 6 wt. % (based on weight of themodified starch) and a viscosity of 10,000 to 100,000 mPa·s (in a 43 wt.% aqueous solution, Brookfield viscometer, spindle #7 at 20° C. and 20rpm).

For the above-stated embodiments, the preferred features of the agentaccording to the invention apply mutatis mutandis, as do in particularthe quantities used.

In addition to starch modified with propylene oxide (particularly thatmodified with propylene oxide according to embodiments A) to R)), thecosmetic agent according to the invention preferably also contains atleast one polymer chosen from film-forming polymers or setting polymers.In this way, it is possible, for example, to finely tune the reshapingresult and conditioning of the fibers. These additional polymers differfrom starches modified with propylene oxide and can have an anionic,amphoteric, nonionic, permanently cationic or temporarily cationic(preferably nonionic, permanently cationic or temporarily cationic)charge.

Polymers according to the invention refer to compounds synthesized froma plurality of molecules wherein one kind or a plurality of species ofatoms or atomic groups (“constitutive units”, “basic building blocks” or“repeat units”) is repeatedly arranged adjacent one another and have amolecular weight of at least 10,000 g/mol. The polymers are obtained bypolyreaction, which can proceed artificially (i.e., synthetically) ornaturally.

Film-forming polymers refer to those polymers which, on drying, leavebehind a continuous film on the skin, hair or nails. Such film formerscan be used in a wide variety of cosmetic products, such as face masks,make-up, hair fixatives, hairsprays, hair gels, hair waxes, hair tonics,shampoos or nail polishes. Particular preference is given to thosepolymers having sufficient solubility in water, alcohol or water/alcoholmixtures. Thus, corresponding solutions can be produced which may besimply applied or further processed.

Film-forming polymers further refer to those polymers capable of, whenapplied in a 0.01 to 20 wt. % aqueous, alcoholic or aqueous-alcoholicsolution, depositing a transparent polymer film on the hair.

Hair-setting polymers assist in holding or building up the volume andfullness of the overall hairstyle. These polymers are simultaneouslyalso film-forming polymers and therefore generally typical substancesfor shaping hair treatment agents such as hair setting preparations,hair mousses, hair waxes, and hair sprays. Film formation in thisrespect can occur only at points and connect only a few fibres together.

Additional cationic film-forming and/or cationic setting polymers can bechosen from cationic, quaternized cellulose derivatives. Cationic,quaternized celluloses which are advantageous for the purposes of theinvention are generally those having more than one permanent cationiccharge in a side chain.

Among these, emphasis should be placed on those cationic cellulosederivatives produced by reaction of hydroxyethylcellulose with adimethyldiallylammonium reactant (particularly dimethyldiallylammoniumchloride), optionally in the presence of further reactants. Among thesecationic celluloses, cationic celluloses which are particularly suitableare those with the INCI name Polyquaternium-4, distributed, for example,under the names Celquat® H 100, Celquat® L 200 by National Starch.

Additional cationic film-forming and/or cationic setting polymers whichare suitable are those having at least one structural unit of formula(M-I) and at least one structural unit of the formula (M-VI), andoptionally at least one structural unit of the formula (M-V)

whereinR¹ and R⁴ are, mutually independently, a hydrogen atom or a methylgroup,A¹ and A² are, mutually independently, a 1,2-ethanediyl, 1,3-propanediylor 1,4-butanediyl group,R², R³, R⁵ and R⁶ are, mutually independently, a (C₁ to C₄) alkyl group,andR⁷ is a (C₈ to C₃₀) alkyl group.

The positive charge of monomer (M-VI) can be offset using any possiblephysiologically acceptable anions, such as chloride, bromide,hydrogensulfate, methylsulfate, ethylsulfate, tetrafluoroborate,phosphate, hydrogenphosphate, dihydrogenphosphate or p-toluenesulfonate,triflate. Suitable compounds are, for example, commercially available as

-   -   copolymers of diethylsulfate-quaternized        dimethylaminoethylmethacrylate methosulfate with        vinylpyrrolidone with the INCI name Polyquaternium-11 under the        names Gafquat® 440, Gafquat®734, Gafquat®755 (in each case ISP)        and Luviquat PQ 11 PN (BASF SE),    -   copolymers of methacryloylaminopropyllauryldimethylammonium        chloride with vinylpyrrolidone and        dimethylaminopropylmethacrylamide with the INCI name        Polyquaternium-55 under the trade names, Styleze® W-10, Styleze®        W-20 (ISP),    -   copolymers of N-vinylpyrrolidone, N-vinylcaprolactam,        N-(3-dimethylaminopropyl)-methacrylamide and        3-(methacryloyl)propyllauryldimethylammonium chloride (INCI        name: Polyquaternium-69) under the trade name AquaStyle® 300        (28-32 wt. % active substance in ethanol-water mixture) (ISP).

Additional film-forming and/or setting polymers chosen from cationicpolymers having at least one structural unit comprising a permanentlycationized nitrogen atom which may particularly be used in the inventionare those cationic film-forming and/or cationic setting polymers havingat least one structural element of the formula (M1)

wherein R″ is a (C₁ to C₄) alkyl group, particularly a methyl group, andadditionally have at least one further cationic and/or nonionicstructural element.

The positive polymer charge of the component can be offset using anypossible physiologically acceptable anions, such as chloride, bromide,hydrogensulfate, methylsulfate, ethylsulfate, tetrafluoroborate,phosphate, hydrogenphosphate, dihydrogenphosphate or p-toluenesulfonate,triflate.

It is preferred for the cosmetic agent according to the invention toadditionally contain as the cationic film-forming and/or cationicsetting polymer at least one copolymer (b1) which, in addition to atleast one structural element of formula (M1), additionally contains astructural element of formula (M-I)

wherein R″ is a (C₁ to C₄) alkyl group, particularly a methyl group.

The positive polymer charge of copolymers (b1) can be offset using anypossible physiologically acceptable anions, such as chloride, bromide,hydrogensulfate, methylsulfate, ethylsulfate, tetrafluoroborate,phosphate, hydrogenphosphate, dihydrogenphosphate or p-toluenesulfonate,triflate.

Cationic film-forming and/or cationic setting polymers which are veryparticularly preferred as copolymers (b1) contain 10 to 30 mol %,preferably 15 to 25 mol % and particularly 20 mol % of structural unitsaccording to formula (M1) and 70 to 90 mol %, preferably 75 to 85 mol %and particularly 80 mol % of structural units according to formula(M-I).

Here, it is particularly preferred for copolymers (b1) to contain, inaddition to polymer units occurring from the incorporation of structuralunits according to formula (M1) and (M-I) into the copolymer, up to 5wt. %, preferably at most 1 wt. %, of polymer units originating from theincorporation of other monomers. Copolymers (b1) are preferablyexclusively synthesized from structural units of formula (M1) withR″=methyl, and (M-I) and can be described by the general formula (Poly1)

wherein m and p vary depending on the molar mass of the polymer and arenot intended to imply that the copolymers are block copolymers. Instead,structural units of formula (M1) and formula (M-I) can be randomlydistributed in the molecule.

If a chloride ion is used to offset the positive charge of the polymerof formula (Polyl), such N-methylvinylimidazole/vinylpyrrolidonecopolymers are designated according to INCI nomenclature asPolyquaternium-16 and are obtainable, for example, from BASF under thetrade names Luviquat® Style, Luviquat® FC 370, Luviquat®FC 550,Luviquat®FC 905 and Luviquat®MQ 552.

If a methosulfate is used to offset the positive charge of the polymerof the formula (Poly1), such N-methylvinylimidazole/vinylpyrrolidonecopolymers are designated according to INCI nomenclature asPolyquaternium-44 and are obtainable, for example, from BASF under thetrade name Luviquat® UltraCare.

In addition to or instead of copolymer(s) (b1), cosmetic agentsaccording to the invention can also contain copolymers (b2) which, basedon copolymer (b1), comprise structural units of formula (M-II) asadditional structural units

Further cosmetic agents which are particularly preferred according tothe invention contain as cationic film-forming and/or cationic settingpolymer at least one copolymer (b2) having at least one structural unitaccording to formula (M1-a), at least one structural unit according toformula (M-I) and at least one structural unit according to formula(M-II)

Here, it is particularly preferred for copolymers (b2) to contain, inaddition to polymer units which arise from the incorporation of thestated structural units according to formula (M1-a), (MI) and (M-II)into the copolymer, up to 5 wt. %, preferably at most 1 wt. %, ofpolymer units originating from the incorporation of other monomers.Copolymers (b2) are preferably exclusively synthesized from structuralunits of the formulae (M1-a), (M-I) and (M-II) and can be described bythe general formula (Poly2)

wherein m, n and p vary depending on the molar mass of the polymer andare not intended to imply that the copolymers are block copolymers.Instead, structural units of the formulae may be present randomlydistributed in the molecule.

The positive polymer charge of component (b2) can be offset using anypossible physiologically acceptable anions, such as chloride, bromide,hydrogensulfate, methylsulfate, ethylsulfate, tetrafluoroborate,phosphate, hydrogenphosphate, dihydrogenphosphate or p-toluenesulfonate,triflate.

If a methosulfate is used to offset the positive charge of the polymerof the formula (Poly2), suchN-methylvinylimidazole/vinylpyrrolidone/vinylcaprolactam copolymers aredesignated according to INCI nomenclature as Polyquaternium-46 and areobtainable, for example, from BASF under the trade name Luviquat® Hold.

Very particularly preferred copolymers (b2) contain 1 to 20 mol %,preferably 5 to 15 mol % and particularly 10 mol % of structural unitsaccording to formula (M1-a) and 30 to 50 mol %, preferably 35 to 45 mol% and particularly 40 mol % of structural units according to formula (I)and 40 to 60 mol %, preferably 45 to 55 mol % and particularly 60 mol %of structural units according to formula (M-II).

In addition to or instead of copolymer(s) (b1) and/or (b2), cosmeticagents according to the invention can also contain copolymers (b3) as afilm-forming cationic and/or setting cationic polymer, whereincopolymers (b3) contain as structural units those of formulae (M1-a) and(I) together with further structural units from the group ofvinylimidazole units and further structural units from the group ofacrylamide and/or methacrylamide units.

Further particularly preferred cosmetic agents contain as cationicfilm-forming and/or cationic setting polymer at least one copolymer (b3)having at least one structural unit according to formula (M1-a), atleast one structural unit according to formula (M-I), at least onestructural unit according to formula (M-VII), and at least onestructural unit according to formula (M-VIII)

Here, it is particularly preferred for copolymers (b3) to contain, inaddition to polymer units arising from the incorporation of thestructural units according to formulae (M1-a), (M-I), (M-VII) and(M-VIII) into the copolymer, up to 5 wt. %, preferably at most 1 wt. %,of polymer units originating from the incorporation of other monomers.Copolymers (b3) are preferably exclusively synthesized from structuralunits of formulae (M1-a), (M-I), (M-VII) and (M-VIII) and can bedescribed by general formula (Poly3)

wherein m, n, o and p vary depending on the molar mass of the polymerand are not intended to imply that the copolymers are block copolymers.Instead, structural units of formulae (M1-a), (M-I), (M-VII) and(M-VIII) can be present randomly distributed in the molecule.

The positive polymer charge of component (b2) can be offset using anypossible physiologically acceptable anions, such as chloride, bromide,hydrogensulfate, methylsulfate, ethylsulfate, tetrafluoroborate,phosphate, hydrogenphosphate, dihydrogenphosphate or p-toluenesulfonate,triflate.

If a methosulfate is used to offset the positive charge of the polymerof the formula (Poly3), suchN-methylvinylimidazole/vinylpyrrolidone/vinylimidazole/methacrylamidecopolymers are designated according to INCI nomenclature asPolyquaternium-68 and are obtainable, for example, from BASF under thetrade name Luviquat® Supreme.

Very particularly preferred copolymers (b3) contain 1 to 12 mol %,preferably 3 to 9 mol % and in particular 6 mol % of structural unitsaccording to formula (M1-a) and 45 to 65 mol %, preferably 50 to 60 mol% and particularly 55 mol % of structural units according to formula(M-I) and 1 to 20 mol %, preferably 5 to 15 mol % and particularly 10mol % of structural units according to formula (M-VII) and 20 to 40 mol%, preferably 25 to 35 mol % and particularly 29 mol % of structuralunits according to formula (M-VIII).

Among additional film-forming cationic and/or setting polymers chosenfrom cationic polymers with at least one structural element of formula(M1), the following are considered preferred:

-   -   vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium chloride        copolymers (such as that with the INCI name Polyquaternium-16        under the trade names Luviquat® Style, Luviquat® FC 370,        Luviquat®FC 550, Luviquat®FC 905 and Luviquat® MQ 552 (BASF        SE)),    -   vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium methylsulfate        copolymers (such as that with the INCI name Polyquaternium-44        under the trade name Luviquat® Care (BASF SE)),    -   vinylpyrrolidone/vinylcaprolactam/1-vinyl-3-methyl-1H-imidazolium        terpolymer (such as that with the INCI name Polyquaternium-46        under the trade names Luviquat® Care or Luviquat® Hold (BASF        SE)),    -   vinylpyrrolidone/methacrylamide/vinylimidazole/1-vinyl-3-methyl-1H-imidazolium        methylsulfate copolymer (such as that with the INCI name        Polyquaternium-68 under the trade name Luviquat® Supreme (BASF        SE)),        and mixtures of these polymers.

In a preferred embodiment, cosmetic agents according to the inventioncontain as additional film-forming and/or setting polymer at least onefilm-forming nonionic and/or setting nonionic polymer.

According to the invention, a nonionic polymer refers to a polymerwhich, in a protic solvent under standard conditions, has substantiallyno structural units with permanently cationic or anionic groups whichhave to be offset by counterions to obtain electroneutrality. Cationicgroups include quaternized ammonium groups but not protonated amines.Anionic groups include carboxylic and sulfonic acid groups.

Film-forming nonionic and/or setting nonionic polymers are present inthe agent preferably in an amount of 0.1 wt. % to 20.0 wt. %, morepreferably 0.2 wt. % to 15.0 wt. %, very preferably 0.5 wt. % to 5.0 wt.%, based on total weight of the cosmetic agent.

Film-forming nonionic and/or setting nonionic polymers are preferablychosen from at least one polymer from

-   -   homopolymers and nonionic copolymers of N-vinylpyrrolidone,    -   nonionic copolymers of isobutene,    -   nonionic copolymers of maleic anhydride.

A preferred combination of film-forming nonionic and/or setting nonionicpolymers is one comprising at least one nonionic copolymer of maleicanhydride and at least one polymer from homopolymers and nonioniccopolymers of N-vinylpyrrolidone.

Suitable polyvinylpyrrolidones include commercial products such asLuviskol® K 90 or Luviskol® K 85 from BASF SE.

Suitable polyvinyl alcohols are distributed, for example, under thetrade names Elvanol® by Du Pont or Vinol® 523/540 by Air Products.

Suitable polyvinyl acetate is distributed, for example, under the tradename Vinac® as an emulsion by Air Products.

Very particularly preferred agents according to the invention are thosehaving as film-forming nonionic and/or setting nonionic polymer at leastone polymer chosen from

-   -   copolymers of maleic anhydride and methyl vinyl ether,    -   polyvinylpyrrolidone,    -   copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic        acids with 2 to 18 carbon atoms, particularly N-vinylpyrrolidone        and vinyl acetate,    -   copolymers of N-vinylpyrrolidone and N-vinylimidazole and        methacrylamide,    -   copolymers of N-vinylpyrrolidone and N-vinylimidazole and        acrylamide,    -   copolymers of N-vinylpyrrolidone with N,N-di(C₁ to        C₄)-alkylamino-(C₂ to C₄)-alkylacrylamide,    -   copolymers of N-vinylpyrrolidone with N,N-di(C₁ to        C₄)-alkylamino-(C₂ to C₄)-alkylacrylamide, or mixtures of these        polymers.

It is preferred for the molar ratio of structural units obtained fromthe monomer N-vinylpyrrolidone to structural units obtained from themonomer vinyl acetate of the polymer to be in a range from 20:80 to80:20, particularly from 30:70 to 60:40.

Suitable copolymers of vinylpyrrolidone and vinyl acetate areobtainable, for example, under the trademark Luviskol® VA 37, Luviskol®VA 55, Luviskol® VA 64 and Luviskol® VA 73 from BASF SE.

Further preferred cosmetic agents according to the inventionadditionally contain as nonionic film-forming and/or nonionic settingpolymer at least one copolymer (n1) having at least one structural unitaccording to formula (M-I), at least one structural unit according toformula (M-VII), and at least one structural unit according to formula(M-VIII)

Here, it is particularly preferred for these copolymers to contain, inaddition to polymer units arising from incorporation of structural unitsaccording to formulae (M1-a), (I), (VII) and (VIII) into the copolymer,up to 5 wt. %, preferably at most 1 wt. %, of polymer units originatingfrom the incorporation of other monomers. Copolymers (n1) are preferablyexclusively synthesized from structural units of formulae (M1-a), (I),(VII) and (VIII) and can be described by the general formula (Poly4)

wherein m, n, o and p vary depending on the molar mass of the polymerand are not intended to imply that the copolymers are block copolymers.Instead, structural units of formulae (I), (VII) and (VIII) can bepresent randomly distributed in the molecule.

One particularly preferred polymer is chosen from polymers having theINCI name VP/Methacrylamide/Vinyl Imidazole Copolymer, obtainable, forexample, under the trade name Luviset Clear from BASF SE.

Further suitable according to the invention are those pulverulentcompositions additionally having at least one nonionic film-formingand/or nonionic setting polymer comprising at least one structural unitof formula (M-I) and at least one structural unit of formula (M-III)

whereinR¹ is a hydrogen atom or a methyl group,X¹ is an oxygen atom or an NH group,A¹ is a 1,2-ethanediyl, 1,3-propanediyl or 1,4-butanediyl groupR² and R³ are, mutually independently, a (C₁ to C₄) alkyl group.

It is particularly preferred for the above nonionic film-forming and/ornonionic setting polymer to be chosen from at least one polymer havingat least one or a plurality of the following features:

R¹ is a methyl group,X¹ is an NH group,A¹ is 1,2-ethanediyl or 1,3-propanediyl,R² and R³ are, mutually independently, methyl or ethyl (particularlypreferably methyl).

Additional nonionic film-forming and/or nonionic setting polymer of thisembodiment is particularly preferably at least one polymer having atleast one structural unit of formula (M-I) and at least one structuralunit of formula (M-III-8),

One very particularly preferred additional nonionic film-forming and/ornonionic setting polymer of this embodiment is a copolymer ofN-vinylpyrrolidone and N,N-dimethylaminopropylmethacrylamide, sold, forexample, with the INCI name VP/DMAPA Acrylates Copolymer, for example,under the tradename Styleze® CC 10 by ISP.

Preferred cosmetic agents according to one embodiment are those havingat least one additional film-forming and/or setting polymer, providedthat all these additional polymers are polysaccharide-based polymers.These additional polymers differ from the propylene oxide-modifiedpolysaccharides. It is preferred that all further polymers of thecosmetic agent be chosen from xanthan, dehydroxanthan, alginate, guargum, gum arabic, locust bean gum, starch, chitosan or mixtures thereof.

The additional film-forming and/or setting polymers are preferablypresent in an amount of 0.5 wt. % to 30 wt. %, particularly 2.5 wt. % to20 wt. %, based on weight of the agent.

In order to improve the effects according to the invention, it ispreferably suitable to add at least one compound of formula (II),

HO—CH₂—(CHOH)_(n)—CH₂—OH  (II)

wherein n is an integer from 1 to 4.

Agents according to the invention are particularly effective if theycontain glycerol and/or sorbitol as compounds of formula (II).

An input of compounds of formula (II) in an amount from 0.2 to 10 wt. %,particularly 0.5 to 7 wt. % has proven advantageous.

It is also preferred to use at least one nonionic surfactant. Accordingto the invention, these surfactants can already have an emulsifyingaction.

Nonionic surfactants contain as hydrophilic group, for example, a polyolgroup, a polyalkylene glycol ether group or a combination of a polyolgroup and polyglycol ether group. Such compounds include

-   -   addition products of 2 to 100 mol of ethylene oxide and/or 1 to        5 mol of propylene oxide onto linear or branched fatty alcohols        with 8 to 30 carbon atoms, onto fatty acids with 8 to 30 carbon        atoms and onto alkylphenols with 8 to 15 C atoms in the alkyl        group,    -   addition products of 2 to 20 units of glycerol onto linear or        branched fatty alcohols with 8 to 30 carbon atoms in the alkyl        group, onto linear or branched fatty acids with 8 to 30 carbon        atoms in the alkyl group, such as those grades obtainable under        the commercial names Dermofeel® G 10 LW (Straetmans Chemische        Produkte),    -   addition products, end group-terminated with a methyl or C₂-C₆        alkyl residue, of 2 to 50 mol of ethylene oxide and/or 1 to 5        mol of propylene oxide onto linear and branched fatty alcohols        having 8 to 30 carbon atoms, onto fatty acids having 8 to 30 C        atoms and onto alkylphenols having 8 to 15 C atoms in the alkyl        group, such as the grades obtainable under the commercial names        Dehydrol® LS, Dehydrol® LT (Cognis),    -   C₁₂-C₃₀ fatty acid mono- and diesters of addition products of 1        to 30 mol of ethylene oxide onto glycerol,    -   addition products of 5 to 60 mol of ethylene oxide onto castor        oil and hardened castor oil,    -   polyol fatty acid esters, such as the commercial product        Hydagen® HSP (Cognis) or Sovermol grades (Cognis),    -   alkoxylated triglycerides,    -   alkoxylated fatty acid alkyl esters of the formula (E4-I)

R¹CO−(OCH₂CHR²)_(w)OR³  (E4-I)

-   -   wherein R¹CO is a linear or branched, saturated and/or        unsaturated acyl residue having 6 to 22 carbon atoms, R² is        hydrogen or methyl, R³ is linear or branched alkyl residues        having 1 to 4 carbon atoms and w is a number from 1 to 20,    -   amine oxides,    -   hydroxy mixed ethers described, for example, in German Patent        Application No. 19738866,    -   sorbitan fatty acid esters and addition products of ethylene        oxide onto sorbitan fatty acid esters such as polysorbates,    -   sugar fatty acid esters and addition products of ethylene oxide        onto sugar fatty acid esters,    -   addition products of ethylene oxide onto fatty acid        alkanolamides and fatty amines,    -   sugar surfactants of the alkyl and alkenyl oligoglycoside type        of the formula (E4-II),

R⁴O-[G]_(p)  (E4-II)

-   -   wherein R⁴ is an alkyl or alkenyl residue having 4 to 22 carbon        atoms, G is a sugar residue having 5 or 6 carbon atoms and p is        a number from 1 to 10. They may be obtained according to        relevant methods of preparative organic chemistry.

Suitable nonionic surfactants which are particularly preferred for usein the agent according to the invention are those chosen from

-   -   addition products of 2 to 20 units of glycerol onto linear or        branched fatty alcohols with 8 to 30 carbon atoms in the alkyl        group,    -   addition products of 2 to 20 units of glycerol onto linear or        branched fatty acids with 8 to 30 carbon atoms in the alkyl        group,    -   sugar surfactants of the alkyl and alkenyl oligoglycoside type        according to formula (E4-II) above, and        mixtures of these surfactants.

Nonionic surfactants are preferably present in the agent according tothe invention in an amount of 0.005 wt. % to 10 wt. %, particularly 0.01to 2 wt. %, based on weight of the agent.

Agents according to the invention can also contain at least one plantextract. Typically, these extracts are produced by extraction of theentire plant. However, in individual cases it may be preferable toproduce the extracts solely from the blossoms and/or leaves of theplant. Suitable plant extracts are obtained by extraction with organicsolvents (e.g., ethanol, isopropanol, diethyl ether, petroleum ether,benzene, chloroform) or by steam distillation. According to theinvention, preference is given to extracts from bamboo, linseed, waterlily, green tea, oak bark, stinging nettle, witch hazel, hops, henna,chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, Aloevera, pine-needle, horse chestnut, sandalwood, juniper, coconut, mango,apricot, lime, wheat, kiwi fruit, melon, orange, grapefruit, sage,rosemary, birch, mallow, lady's smock, wild thyme, yarrow, thyme,melissa, restharrow, coltsfoot, marsh mallow, meristem, ginseng andginger root. The additional plant extract is preferably present in theagent in an amount of 0.05 wt. % to 1.0 wt. %, particularly 0.1 wt. % to0.5 wt. %, based on weight of the cosmetic agent.

It is preferred in particular if the agent according to the invention isformulated as a cream so that the cosmetic agent according to theinvention additionally contains at least one oil phase.

An oil phase according to the invention refers to a phase which isliquid at 20° C. and which, at 20° C., dissolves in an amount of lessthan 1 g in 100 g of water.

The oil phase preferably has a viscosity of up to 1,000 mPa·s,(Brookfield, RVDV II+, 20° C., 20 revolutions per minute, spindle no.1).

In a preferred embodiment, the oil of the oil phase is chosen from atleast one oil of

-   -   plant oils,    -   animal oils,    -   ester oils,    -   liquid fatty acids and/or the mono-, di- and trifatty acid        esters of saturated and/or unsaturated linear and/or branched C₆        to C₂₂ fatty acids with glycerol.

Preferred vegetable oils are chosen from at least one of amaranth oil,sunflower oil, olive oil, soy oil, rapeseed oil, castor oil, sesame oil,almond oil, jojoba oil, orange oil, apricot kernel oil, macadamia nutoil, wheat germ oil, peach stone oil and the liquid fractions of coconutoil.

Preferred ester oils are chosen from esters of C₆-C₃₀ fatty acids withC₂-C₃₀ fatty alcohols. Monoesters of fatty acids with alcohols having 2to 24 C atoms are preferred. Examples of fatty acid moieties used in theesters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capricacid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid,palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidicacid, petroselinic acid, linoleic acid, linolenic acid, elaeostearicacid, arachidic acid, gadoleic acid, behenic acid and erucic acid andthe technical mixtures thereof, which are obtained, for example, onpressure splitting of natural fats and oils, on oxidation of aldehydesfrom Roelen's oxo synthesis or the dimerization of unsaturated fattyacids. Examples of fatty alcohol moieties in the ester oils areisopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexylalcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristylalcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearylalcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolylalcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol,gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcoholand the technical mixtures thereof, which are obtained, for example, onhigh pressure hydrogenation of technical methyl esters based on fats andoils or aldehydes from Roelen's oxo synthesis and as a monomer fractionon the dimerization of unsaturated fatty alcohols. Particularlypreferred substances according to the invention are isopropyl myristate(Rilanit® IPM), isononanoic acid C₁₆₋₁₈ alkyl ester (Cetiol® SN),2-ethylhexyl palmitate (Cegesoft® 24), stearic acid 2-ethylhexyl ester(Cetiol® 868), cetyl oleate, glycerol tricaprylate, coconut fattyalcohol caprinate/caprylate (Cetiol® LC), n-butyl stearate, oleylerucate (Cetiol® J 600), isopropyl palmitate (Rilanit® IPP), oleyloleate (Cetiol®), lauric acid hexyl ester (Cetiol® A), di-n-butyladipate (Cetiol® B), myristyl myristate (Cetiol® MM), cetearylisononanoate (Cetiol® SN), oleic acid decyl ester (Cetiol® V).

Mono-, di- and trifatty acid esters of saturated and/or unsaturatedlinear and/or branched fatty acids with glycerol which are preferablyusable as oil in the oil phase are triglyceride esters of capric acidand caprylic acid (INCI name: Caprylic/Capric Triglyceride), forexample, obtainable as a commercial product from Cognis under the nameMyritol® 312.

The additional oil phase is preferably present in the agent according tothe invention in an amount of 0.05 wt. % to 25 wt. %, particularly 0.1wt. % to 20 wt. %, based on weight of the cosmetic agent.

Agents according to the invention which additionally contain at leastone fatty substance are also suitable.

According to the invention, fatty substances are those compounds which,at 20° C., are soluble in an amount of less than 1 g in 100 g of water.

The fatty substance is preferably chosen from candelilla wax, sheabutter, carnauba wax, beeswax, coconut oil, C₁₂ to C₂₀ fatty acids(particularly palmitic acid, stearic acid).

The additional fatty substance is preferably present in the agentaccording to the invention in an amount of 0.05 wt. % to 35 wt. %,particularly of 1 wt. % to 20 wt. %, based on weight of the cosmeticagent.

Agents according to the invention contain their active ingredients in acosmetic carrier, preferably in a hydrous cosmetic carrier, alcoholiccosmetic carrier or an aqueous-alcoholic cosmetic carrier. Fortemporarily reshaping hair, such carriers include lotions, water-in-oilemulsions, oil-in-water emulsions, creams, gels, foams, pomades, waxesor other preparations suitable for use on hair.

For the present invention, aqueous-alcoholic carriers include aqueouscompositions containing 3 to 70 wt. % of a C₁-C₄ alcohol, particularlyethanol or isopropanol. The agents can also contain further organicsolvents such as methoxybutanol, benzyl alcohol, diethylene glycolmonoethyl ether, 1,2-propylene glycol or 1,3-propylene glycol. Anywater-soluble organic solvents are preferred.

A cationic surfactant can be used as a conditioner. Here, preference isgiven to cationic surfactants such as quaternary ammonium compounds,ester quats and the amidoamines. Preferred quaternary ammonium compoundsare ammonium halides, particularly chlorides and bromides such asalkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides andtrialkylmethylammonium chlorides (e.g., cetyltrimethylammonium chloride,stearyltrimethylammonium chloride, distearyldimethylammonium chloride,lauryldimethylammonium chloride, lauryldimethylbenzylammonium chlorideand tricetylmethylammonium chloride), and the imidazolinium compoundsknown under the INCI names Quaternium-27 and Quaternium-83. Long alkylchains of these surfactants preferably comprise 10 to 18 carbon atoms.Since, however, addition of surface-active substances can have anegative effect on the hydrophobic properties of hydrophobized silicondioxide and thus on the stability of the cosmetic agent, the amount ofconditioning surfactant has to be carefully matched to totalcomposition. Preferably, no surfactant components are added.

Moreover, at least one vitamin, one provitamin, one vitamin precursorand/or of one of the derivatives thereof can be used as conditioner.

Preferred vitamins, provitamins and vitamin precursors according to theinvention are those conventionally assigned to the groups A, B, C, E, Fand H. Particularly preferred vitamins are those belonging to the Bgroup or to the vitamin B complex, very particularly preferably vitaminB₅ (pantothenic acid, panthenol and pantolactone).

A series of carboxylic acids are also suitable as conditioner.

Short-chain carboxylic acids in particular can be advantageous. For thepurposes of the invention, short-chain carboxylic acids and thederivatives thereof are carboxylic acids which can be saturated orunsaturated and/or linear or branched or cyclic and/or aromatic and/orheterocyclic and have a molecular weight of less than 750. Preferencemay be given to saturated or unsaturated straight-chain or branchedcarboxylic acids with a chain length of from 1 to 16 C atoms in thechain, very particularly those with a chain length of from 1 to 12 Catoms.

Further suitable conditioners are protein hydrolysates and/or thederivatives thereof, use of protein hydrolysates of plant origin (e.g.,soy, almond, pea, potato and wheat protein hydrolysates) beingpreferred. Such products are obtainable, for example, under thetradenames Gluadin® (Cognis), DiaMin® (Diamalt), Lexein® (Inolex),Hydrosoy® (Croda), Hydrolupin® (Croda), Hydrosesame® (Croda),Hydrotritium® (Croda) and Crotein® (Croda).

Although use of protein hydrolysates as such is preferred, amino acidmixtures obtained in other ways can also optionally be used in theirplace. It is also possible to use derivatives of protein hydrolysates,for example, in the form of the fatty acid condensation productsthereof. Such products are distributed, for example, under the namesLamepon® (Cognis), Lexein® (Inolex), Crolastin® (Croda), Crosilk®(Croda) or Crotein® (Croda).

The teaching according to the invention comprises all isomeric forms,such as cis-trans isomers, diastereomers and chiral isomers.

According to the invention, it is also possible to use a mixture of aplurality of protein hydrolysates.

Furthermore, lipids and oil bodies are suitable as conditioners, forexample, plant oils, liquid paraffin oils, isoparaffin oils, synthetichydrocarbons and ester oils, enzymes and pearl extracts.

With addition of a UV filter, both the preparations themselves and thetreated fibers can be protected from the harmful effects of UVradiation. It may therefore be advantageous to also add at least one UVfilter to the cosmetic agent. Suitable UV filters are not subject to anygeneral restrictions regarding structure and physical properties.Rather, any UV filters usable in the field of cosmetics whose absorptionmaximum is in the UVA (315-400 nm), the UVB (280-315 nm) or the UVC(<280 nm) range are suitable. UV filters with an absorption maximum inthe UVB range, particularly from approx. 280 to approx. 300 nm, areparticularly preferred.

Preferred UV filters according to the invention can be chosen fromsubstituted benzophenones, p-aminobenzoic acid esters, diphenylacrylicacid esters, cinnamic acid esters, salicylic acid esters, benzimidazolesand o-aminobenzoic acid esters. Examples which may be mentioned here are2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the sodium saltthereof (benzophenone-4; Uvinul®MS 40; Uvasorb®S 5).

In one particular embodiment, the cosmetic agent contains one or moredirect dyes. This makes it possible, when applying the composition, forthe treated keratin fibers not only to be temporarily structured butalso to be dyed at the same time. This may be particularly desirablewhen, for example, only temporary dyeing with conspicuous fashion colorsis desired, which can be removed again from the keratin fibers simply bywashing.

Cosmetic agents according to the invention can also contain alkalizingagents, conventionally alkali metal or alkaline earth metal hydroxides,ammonia or organic amines. Preferred alkalizing agents aremonoethanolamine, monoisopropanolamine, 2-amino-2-methylpropanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,2-amino-2-methylbutanol and triethanolamine and alkali metal andalkaline earth metal hydroxides. In particular, monoethanolamine,triethanolamine and 2-amino-2-methylpropanol and2-amino-2-methyl-1,3-propanediol are preferred in the context of thisgroup. ω-Amino acids such as ω-aminocaproic acid can also be used asalkalizing agents.

The present invention secondly provides for use of a cosmetic agent ofthe first subject matter of the invention for temporarily reshapingand/or setting the shape of keratin fibers, particularly human hair.

The present invention thirdly provides a method for temporarilyreshaping keratin fibers, particularly human hair, wherein a cosmeticagent of the first subject matter of the invention is applied onto thekeratin fibres.

It is preferable if, after exposure to the cosmetic agent of the firstsubject matter of the invention, the keratin fibers are not rinsed andare left on the fibers.

The following Examples are intended to explain the subject matter of thepresent invention without limiting it in any way.

EXAMPLES

Unless stated otherwise, all quantities in this Examples section arestated in weight percent. The following formulations were prepared:

Example 1.1 “Hair Mousse”

Raw material E1[wt. %] E2[wt. %] Hydagen HCMF ¹ 0.50 — Polyquaternium-4— 0.30 Polyquaternium-11 — 1.50 Lactic acid 0.28 — Luviskol 60/40 W NP ²10.70 — Nonionic starch modified with propylene oxide ³ 2.70 2.00 Sodiumbenzoate 0.30 — D-Panthenol 0.15 0.15 Dow Corning 939 ⁴ 0.20 0.20Dehyquart A CA ⁵ 1.00 1.00 PEG-40 Hydrogenated Castor Oil — 0.30Glycerol — 0.15 Propane/butane 8.00 8.00 Water Ad 100 Ad 100 ¹ chitosan(80% deacetylated), molecular weight 50,000 to 1,000,000 g/mol, Cognis ²copolymer of N-vinylpyrrolidone and vinyl acetate, ³ potato starch,propylene oxide content: 4 wt. % propylene oxide, viscosity: 64,000 mPa· s, average molecular weight (weight-average): 800 kDa ⁴ approximately32-36% active substance, INCI name: Amodimethicone, Trideceth-12,Cetrimonium Chloride (Dow Corning) ⁵ trimethylhexadecylammonium chloride(approximately 24-26% active substance; INCI name: Aqua (Water),Cetrimonium Chloride) (Cognis)

The respective formulation ingredients except for the propellant weremixed and the mixture introduced into an aerosol container satisfyingthe following industrial parameters: aluminum reservoir with valveproduct 522983 PV10697 from Precision (Deutsche Präzisions-Ventil GmbH).The aerosol can was appropriately sealed and the propellant introduced.

Example 1.2 “Hair Gels”

Raw material E4 E5 E6 E7 Disodium EDTA — — 0.05 — 1,2-Propanediol 6.00 —— — Starch modified with propylene 8.50 10.00 10.00 3.00 oxide ⁶Methylparaben 0.10 — — — Aculyn 28 ⁷ 3.00 — — — Aculyn 88 ⁸ — — — 1.80Synthalen W 2000 ⁹ — — — 1.50 Polygel W 30 ¹⁰ — 3.00 — — Structure 2001¹¹ — — 5.00 — PEG-40 Hydrogenated Castor Oil 0.40 — — 0.20PPG-5-Ceteth-20 — — 0.50 — Euxyl K320 ¹² — — — 1.00 Luviskol K 90 ¹³ — —12.00 — Luviskol K 85 ¹⁴ — 5.00 — — Polyethylene glycol 1500 2.00 — — —Glycerol 10.00 2.75 2.00 — D-Panthenol 0.15 — 0.20 0.20 Neolone PE 0.300.60 0.60 Triethanolamine — — — 0.80 Lactic acid — 0.10 0.30 — UvinulP25 ¹⁵ — — — 0.05 Perfume 0.15 0.20 0.20 0.20 Water Ad 100 Ad 100 Ad 100Ad 100 ⁶ potato starch modified with 4.5 wt. % propylene oxide; averagemolecular weight 800 kDa, viscosity of a 43 wt. % solution in water64,000 mPa · s ⁷ copolymer of (meth)acrylic acid, (meth)acrylic acidester and beheneth-25 methacrylic acid ester (19-21 wt. % solids contentin water; INCI name: Acrylates/Beheneth-25 Methacrylate Copolymer) (Rohm& Haas) ⁸ copolymer of (meth)acrylic acid, (meth)acrylic acid ester andsteareth-20 methacrylic acid ester (28-33 wt. % solids content in water;INCI name: Acrylates/Steareth-20 Methacrylate Copolymer) (Rohm & Haas) ⁹copolymer of (meth)acrylic acid, (meth)acrylic acid ester and palmeth-25methacrylic acid ester (30-32 wt. % solids content in water; INCI name:Acrylates/Palmeth-25 Methacrylate Copolymer) (3 V Sigma) ¹⁰ copolymer of(meth)acrylic acid, (meth)acrylic acid ester and palmeth-25 itaconicacid ester (30 wt. % solids content in water; INCI name:Acrylates/Palmeth-25 Itaconate Copolymer) (3 V Sigma) ¹¹ copolymer of(meth)acrylic acid, (meth)acrylic acid ester and steareth-20 itaconicacid ester (30 wt. % solids content in water; INCI name:Acrylates/Steareth-20 Itaconate Copolymer) (3 V Sigma) ¹² mixture ofphenoxyethanol, methylparaben, ethylparaben, propylene glycol (Schülke &Mayr) ¹³ polyvinylpyrrolidone (approx. 20% solids content in water; INCIname: PVP) (BASF) ¹⁴ polyvinylpyrrolidone (approx. 20% solids content inwater; INCI name: PVP) (BASF) ¹⁵ 4-aminobenzoic acid ethyl ester + 25mol ethylene oxide (INCI name: PEG-25 PABA) (BASF SE)

2.0 Proof of Action

The following starches modified with propylene oxide were used:

TABLE 1 Propylene oxide-modified starches - Average molecular Viscosityrange Name of the weight range of the of the modified modified starchmodified starch (kDa) starch [mPa · s] HPS A ¹⁶ 700-900 40,000-70,000HPS B ¹⁷ 700-900 40,000-70,000 HPS C ¹⁸ 700-900 40,000-70,000 ¹⁶ tapiocastarch modified with 4.5-5.5 wt. % propylene oxide ¹⁷ tapioca starchmodified with 9.5-10.5 wt. % propylene oxide ¹⁸ tapioca starch modifiedwith 19-21 wt. % propylene oxide

Polymer solutions in water, each of 5 wt. % strength of the respectivehydroxypropyl starches HPS A to C, of polyvinylpyrrolidone (PVP)(Luviskol® K 85, BASF SE) and of polyvinylpyrrolidone/vinyl acetatecopolymer (PVP/VA) (Luviskol® 64 W NP, BASF SE) were produced. Curlretention measurements were then carried out on strands of hair treatedtherewith. Here, strands of hair were investigated according to theprocedure described in 3.0 for determining High Humidity Curl Retention(HHCR).

The following results were obtained:

TABLE 2 High humidity curl retention (HHCR) - Polymer solution HHCR HPSA - 5 wt. % 90% HPS A - 5 wt. % 65% HPS A - 5 wt. % 75% PVP/VA - 5 wt. %26% PVP - 5 wt. % 23%

The strands of hair treated with agents according to the inventionexhibited hairstyle retention which was more resistant to atmospherichumidity. Better HHCR values and better styling hold were obtained whencarrying out similar experiments with correspondingly modified potatostarch.

3.0 Performance of High Humidity Curl Retention Measurement

Standardized strands of hair from Kerling (item no. 827560) of the“European Natural”, color 6/0 type) of a length (L_(max)) of 220 mm anda weight of 0.6 g were used. The strands were washed with a 12.5 wt. %sodium laureth sulfate solution by way of preparation. The strands ofhair were dried overnight in a drying oven at 318 K.

0.18 g of the compositions were applied onto a strand of hair and rubbedin. The strand was then wound onto a curler (Fripac-medis, diam. 7 mm,item no. D-1203) and dried overnight at room temperature.

The curlers were carefully removed and the strands hung up. The lengthof curls was in each case measured (L₀) and the strands placed in aconditioning cabinet. They were stored there at 294 K and a relativeatmospheric humidity of 85% over a period of 24 h, after which thelength of the curls was remeasured (L_(t)).

Five test strands per composition were correspondingly treated andmeasured.

High Humidity Curl Retention (HHCR) was calculated according to thefollowing formula and the arithmetic mean of the HHCR values for the 5test strands was determined for each composition:

${HHCR} = \frac{L_{\max} - L_{t}}{L_{\max} - L_{0}}$

1. Cosmetic agent for temporarily reshaping keratin fibers comprising ina cosmetic carrier at least one starch modified with propylene oxide,wherein the modified starch has an average molecular weight(weight-average) of 50 to 2,500 kDa and a propylene oxide content of 4to 6 wt. % based on weight of the modified starch.
 2. Cosmetic agentaccording to claim 1, wherein the modified starch is gelatinized. 3.Cosmetic agent according to claim 1, wherein the modified starch isuncrosslinked.
 4. Cosmetic agent according to claim 1, wherein themodified starch has an average molecular weight (weight-average) of 100to 2,000 kDa.
 5. Cosmetic agent according to claim 1, wherein, in a 43wt. % solution in water, the modified starch has a viscosity from 150 to1,500,000 mPa·s based on Brookfield viscometer with spindle #7 at 20° C.and 20 rpm.
 6. Cosmetic agent according to claim 1, wherein the modifiedstarch is a tapioca starch modified with propylene oxide, a potatostarch modified with propylene oxide, or a mixture thereof.
 7. Cosmeticagent according to claim 1, wherein the modified starch is present in anamount of 0.01 wt. % to 40 wt. %, based on total weight of the agent. 8.Cosmetic agent according to claim 1 further comprising at least onepolymer chosen from film-forming polymers and setting polymers. 9.Cosmetic agent according to claim 1 further comprising at least onecompound of formula (II),HO—CH₂—(CHOH)_(n)—CH₂—OH  (II) wherein n is an integer from 1 to
 4. 10.Cosmetic agent according to claim 1 further comprising at least onepropellant.
 11. Method for temporarily reshaping keratin fiberscomprising applying a cosmetic agent according to claim 1 onto thekeratin fibers.